High efficiency graphene/wide band-gap semiconductor heterojunction solar cells

ABSTRACT

A photovoltaic solar cell apparatus is described herein combining the advantages of several discoveries that address the previously unsolved problem of creating high conversion efficiency solar cells at a low cost. The solar cell designs and underlying principals disclosed herein may be applied in any type of photovoltaic solar power application, such as large scale photovoltaic solar plants, rooftop panels, solar powered electronic devices, and many others.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation of prior application Ser. No.17/028,035, filed Sep. 22, 2020, which is a continuation of priorapplication Ser. No. 16/890,005, filed Jun. 2, 2020, now U.S. Pat. No.10,833,285 B2, which claims benefit of U.S. Provisional Application No.62/856,698, filed Jun. 3, 2019, U.S. Provisional Application No.62/924,805, filed Oct. 23, 2019, and U.S. Provisional Application No.62/937,938, filed Nov. 20, 2019, each of which is hereby incorporatedherein by reference in its entirety.

FIELD

This application relates generally to the generation of electricityusing solar energy.

BACKGROUND

Various modalities of solar energy conversion are used in the art. Forexample, prior systems employ photovoltaic junctions in favor ofconverting sunlight directly into electricity. It is also known toconvert sunlight into heat and to then utilize that heat to generateelectricity. Conversion efficiency, for example, varies amongstdifferent modalities with many posited modalities performing quitepoorly and none achieving high conversion efficiency. Those relativeconversion efficiencies, in turn, quite directly impact the return oninvestment an enterprise can expect to receive for pursuing a givensolar energy conversion system.

Photovoltaic production of electricity, now more than 600 gigawattsglobally, is increasing exponentially and will reach one terawatt in twoor three years. Solar cells are made of a semiconductor material,typically silicon in crystalline solar cells. Traditionally, a solarcell has two layers: an n-type with a high concentration of electrons,and a p-type with a relatively low concentration of electrons. One sideof a solar cell is “doped” with a p type material such as boron, and theother side with an n-type material such as phosphorous, creating asingle p-n junction. When sunlight hits the n-type layer, electrons aredislodged from the n-region and flow through a circuit to the p-region,creating an electrical current that can be captured and used for power.Although non-equilibrium thermodynamic theory predicts that solar cellconversion efficiencies could potentially be as high as 86%, actuallyachieving higher efficiencies presents difficult technical challenges,and solar cells approaching such efficiencies are not now available.

Most solar cells in commercial production today are based on thisarchitecture of a single p-n junction of doped silicon sheets, eithermonocrystalline or polycrystalline silicon. The solar frequency spectrumapproximates that of a black body at 5,800 K. Much of the solarradiation reaching the Earth is composed of photons with energiesgreater than the 1 V band gap of silicon, which represents the minimumenergy required to excite an electron up to a state where it canparticipate in conduction. These photons are absorbed by silicon, buttheir excess energy is converted to heat rather than electrical energy.On the other hand, much of the solar radiation is composed of photons inthe infrared region of the solar spectrum whose energies are below theband gap of silicon. These cannot be absorbed by silicon thus furtherdecreasing the conversion efficiency of silicon solar cells. Due tothese limitations, today's solar cells consisting primarily of silicontypically convert only about 15%-20% of the energy in sunlight toelectricity. Silicon solar panels are also less effective at hightemperatures. Heterojunction solar cells consisting of a crystallinesilicon cell sandwiched between two layers of amorphous thin filmsilicon have been developed. The additional layers allow more sunlightto be absorbed, allowing efficiencies of 21% or slightly higher to beachieved.

Significant effort has been devoted to the development of solar cellsother than silicon that can overcome the deficiencies discussed above.For example, multijunction solar cells are reported to have thepotential to reach conversion efficiencies of about 45%. Suchmulti-junction solar cells are not made using silicon as asemiconductor. Instead, materials like gallium indium phosphide, indiumgallium arsenide, and germanium are used to create separate layers ofsemiconductors that all respond to different wavelengths of incomingsunlight, making them more efficient at converting sunlight intoelectricity than single-junction cells. While they have the potential tobe several times more efficient than traditional solar cells, suchdesigns are complex and difficult to manufacture and, up to now, highfabrication costs have prevented their being used for large scalecommercialization such as in roof-top or solar electric power plantapplications.

Another prior approach resulting from prior work of the inventor hereofand disclosed in U.S. Pat. Nos. 8,586,999, 8,829,331, and 9,040,395contemplates an array of nanowires comprising a wide band gap materialcore coated with thin graphene shells grown on a foil substrate anddisposed with their longitudinal axes oriented substantially coaxial andparallel to anticipated light beams. These patents postulate that thesolar energy conversion efficiency is enhanced in the nanostructuredradial coaxial shell/core nanowire configuration over conventionalplanar solar cell configurations clue to the strong light absorptionproperties of the graphene and because electron diffusion lengths aremuch shorter. Techniques for growing titanium oxide or silicon carbidenanowire cores are also disclosed, as are methods for coating suchnanowires by high temperature treatment of silicon carbide nanowires orby chemical vapor deposition using a methane environment. These patentsreport an expected cell voltage of the disclosed siliconcarbide/graphene photovoltaic junction solar cell of about 1 V understandard sunlight intensities, which is only marginally higher than thevoltage of conventional silicon solar cells. Because a graphene-basedphotovoltaic junction can be expected to maintain photovoltaicfunctionality at a useful level of energy conversion at hightemperatures that are inhospitable to the functioning of photovoltaicdeices that employ silicon or other materials such as gallium arsenide,the patents focus on co-generation applications in which such cells aredeployed adjacent a second high temperature second modality of solarenergy conversion.

The solar cell technology based on graphene coated nanowire coresdisclosed in the previously referenced patents does not fully addressthe needs of the vast potential market for single modality photovoltaicsolar power generation, such as in photovoltaic solar plants and rooftopsolar panels. To overcome the shortcomings of the conventional siliconbased solar cell technology in those applications, even greaterconversion efficiencies are needed, as are cost effective manufacturingprocedures using readily available materials. Therefore, the inventionof affordable solar cells with conversion efficiencies significantlyhigher than provided by present day technology, and that can beeconomically manufactured on a large scale, would substantially lowersolar electricity costs and facilitate a technological solution to thedetrimental environmental impact resulting from overreliance on fossilfuel energy sources.

BRIEF DESCRIPTION OF THE DRAWINGS

The above needs are at least partially met through an apparatuspertaining to high efficiency solar cells having nanowire cores of awide band gap material and graphene exteriors described in the followingdetailed description, particularly when studied in conjunction with thedrawings, wherein:

FIG. 1 is a perspective view of a portion of a photovoltaic solar cellhaving a plurality of nanowires;

FIG. 1A is a perspective view of one nanowire coated with a shell, asfound in FIG. 1;

FIG. 2 is a cross-sectional view of one form of a photovoltaic solarcell;

FIG. 3 is a cross-sectional view of another form of a photovoltaic solarcell having a masking layer;

FIG. 4 is a cross-sectional view of another form of a photovoltaic solarcell having a multi-component electrode;

FIG. 5 is a top view of one form of a photovoltaic solar cell;

FIG. 6 is a scanning electron microscope image of ZnO nanowire coresgrown on a foil substrate;

FIG. 7 is a scanning electron microscope image of ZnO nanowire coresthat have been coated with reduced graphene oxide;

FIG. 8 is a scanning electron microscope image of ZnO nanowire coresthat have been coated with graphene using a polyaromatic hydrocarbon;

FIG. 9 is Raman spectroscopy results for ZnO nanowire cores that havebeen coated with reduced graphene oxide;

FIG. 10 is Raman spectroscopy results for ZnO nanowire cores that havebeen coated with graphene using a polyaromatic hydrocarbon;

FIG. 11 is a current versus voltage graph for a photovoltaic solar cellhaving ZnO nanowire cores coated with reduced graphene oxide and using asilver electrode in contact with the reduced graphene oxide;

FIG. 12 is a current versus voltage graph for a photovoltaic solar cellhaving ZnO nanowire cores coated with graphene from a polyaromatichydrocarbon and using an indium tin oxide electrode in contact with thegraphene;

FIG. 13 is a current versus voltage graph for a photovoltaic solar cellhaving ZnO nanowire cores coated with graphene from a polyaromatichydrocarbon and using a silver electrode in contact with the graphene;

FIG. 14 is a current versus voltage graph for a photovoltaic solar cellhaving ZnO nanowire cores coated with graphene from a polyaromatichydrocarbon and using an electrode including silver and indium tin oxidein contact with the graphene;

FIG. 15 is graph showing the results of annealing in an oxygenenvironment on the sheet resistance of ZnO nanowires;

FIG. 16 is a graph of normalized current versus illumination wavelengthillustrating wavelength independence of the graphene light absorptioncoefficient;

FIG. 17 is a graph of photo current versus two light intensitiesdiffering by three orders of magnitude for a photovoltaic solar cellhaving ZnO nanowire cores coated with graphene; and

FIG. 18 is a scanning electron microscope image of ZnO nanowire coresgrown on a foil substrate showing both aligned and “flower” type growth.

Elements in the figures are illustrated for simplicity and clarity andhave not necessarily been drawn to scale. For example, the dimensionsand/or relative positioning of some of the elements in the figures maybe exaggerated relative to other elements to help to improveunderstanding of various embodiments of the present invention. Also,common but well-understood elements that are useful or necessary in acommercially feasible embodiment are often not depicted in order tofacilitate a less obstructed view of these various embodiments of thepresent invention. Certain actions and/or steps may be described ordepicted in a particular order of occurrence while those skilled in theart will understand that such specificity with respect to sequence isnot actually required. The terms and expressions used herein have theordinary technical meaning as is accorded to such terms and expressionsby persons skilled in the technical field as set forth above exceptwhere different specific meanings have otherwise been set forth herein.

DETAILED DESCRIPTION

A photovoltaic solar cell apparatus is described herein combining theadvantages of several discoveries that address the previously unsolvedproblem of creating high conversion efficiency solar cells at a lowcost. The solar cell designs and underlying principals disclosed hereinmay be applied in any type of photovoltaic solar power application, suchas large scale photovoltaic solar plants, rooftop panels, solar poweredelectronic devices, solar powered satellites, outdoor lighting, and manyothers.

The photovoltaic effect results in the production of electricitymeasured in watts, the product of current and voltage. The higher thecurrent x voltage product, the higher the cell conversion efficiency.Energy conversion efficiency is measured by dividing the electricalpower output by the incident light power. Factors influencing outputinclude spectral distribution, spatial distribution of power,temperature, and resistive load. IEC standard 61215 is used to comparethe performance of cells at terrestrial temperature: irradiance of 1kW/m2. Specifically, a spectral distribution close to that of solarradiation through AM (airmass) of 1.5 and a cell temperature 25° C. istaken.

The magnitude of the cell current is primarily due to the lightabsorption properties of the cell material and the illuminationintensity. On the other hand, the measured cell voltage is primarily dueto the difference in what are called the “quasi Fermi levels” of themajority charge carriers. In this regard, the work function of amaterial is the minimum thermodynamic energy needed to remove anelectron from a solid to a point in the vacuum immediately outside thesolid surface. Work functions can be measured experimentally and can beshown to be directly related to the Fermi levels of the majoritycarriers. The measured cell voltage is attributed to the effective workfunction of the solar cell, which is the difference in the “workfunctions” of the materials that constitute the photovoltaic junction ofsolar cell.

New insights derived by the applicant based on an intensive andprolonged study of the scientific principles of photovoltaics, led theapplicant to conclude that high conversion efficiency solar cells shouldabsorb the total solar spectrum to provide sizeable short circuitcurrents while constituting materials capable of exhibiting largedifferences in work function so as to be capable of furnishing largeopen circuit potentials. The cell materials should also allow effectivecharge separation at the heterojunction to set the stage for a solarcell having conversion efficiencies several times higher than offered bycurrent technology. Although these conclusions are far fromself-evident, they are not a panacea in and of themselves, for thechoice of materials that would constitute such cells and the elucidationof economical methods for their fabrication present formidablechallenges whose solutions are not at all apparent. The solar cellapparatuses disclosed herein are composed of materials chosen in such away as to provide large photocurrents at high photovoltages andpossessing three or more times the conversion efficiency of currentlyavailable solar cells. The structure and performance of these novelcells as well as the fabrication techniques required for their effectivefunctioning are described here in detail.

In one aspect, the apparatus can comprise, at least in part, a foilsubstrate having a plurality of the coated nanowire cores disposedthereon. The nanowire cores, such as including zinc oxide, are capableof exhibiting large differences in work function relative to the workfunction of the graphene or reduced graphene oxide shells so as to becapable of furnishing large open circuit potentials. To facilitatecharge separation at the graphene-based photovoltaic junction, asubstantially continuous coating of a nonconductive material, such as aninsulator, is formed on the foil substrate between the nanowire cores.The first conducting electrode is electrically connected to the foilsubstrate to provide an electrical pathway to facilitate a movement ofelectrons away from the nanowire cores, and a second conductingelectrode connected to the shells at a second end of the nanowirecore/shell structures provides an electrical pathway to facilitate amovement of positive charges away from the shells.

In another aspect, the photovoltaic solar cell apparatuses herein areprepared by a method that utilizes a hydrothermal synthesis process toform a plurality of nanowire cores, such as of zinc oxide, on a foilsubstrate. In some approaches, at least a majority of the nanowire coresare substantially aligned with one another and generally perpendicularto the foil substrate. In one form, the hydrothermal synthesis processforms a substantially continuous insulator coating, such as ofnonconductive zinc oxide material, on the foil substrate between thenanowire cores. The nanowire cores so formed may be subjected to apost-growth annealing process to reduce structural defects at thesurface of the nanowires cores, which may be effective to improve thediode properties of the nanowire array while also reducing itselectrical resistance.

In yet other aspects, efficient and effective methods are provided forcladding a graphene-based material about a portion of a respectivenanowire core to form a photovoltaic junction. In a preferred form ofthe solar cell apparatus disclosed herein, a single layer of graphene,or no more than a few layers, surrounds the zinc oxide nanowires. Theoutstanding performance of the solar cell apparatus of this embodimentrequires high quality and uniformity of the ultrathin graphene claddingthe zinc oxide nanowires. A novel methodology is disclosed to accomplishthis, which involves forming the graphene shells by thermal conversionfrom at least one polyaromatic hydrocarbon precursor. In anotherapproach, the cladding technique comprises surrounding the nanowirecores with a solution containing graphene oxide followed by thermallyreducing the graphene oxide to form shells of reduced graphene oxideconformally disposed about a portion of a respective nanowire cores.

In one aspect, the graphene side facing away from zinc oxide is incontact with a material that is effective to further lower graphene'swork function. In this manner, the difference in work functions of thematerials constituting the solar cells is increased so as to increasethe built-in potential that determines the open cell voltage. Techniquesfor implementing this enhancement are also disclosed herein. Forexample, the electrode in contact with the graphene-based shells can beformed of a metal, such as silver, that reduces the graphene workfunction when in contact with graphene. In another form, such a metal isprovided as a colloidal suspension within a partially transparentconductive material such as indium tin oxide, to form an electrode thatserves the dual functions of transferring electrical current andenhancing the cell potential by reducing the graphene work function. Soconfigured, the solar cell apparatuses according to the invention canachieve open circuit cell voltages significantly greater than areattainable using conventional silicon based solar cell designs.

These and other cladding methodologies are described in detail below asare the unique and uniquely important optoelectronic properties of thecells. Fabrication techniques, contact doping of graphene, lowering ofcell series resistance, increasing work function differences and othermatters pertaining to maximizing the performance parameters of the newgeneration of solar cells disclosed herein are detailed below. Further,while reference may be made to zinc oxide in many areas herein, itshould be appreciated that other wide band-gap materials may be used inthe alternative and/or in combination with zinc oxide in certain forms.

Turning to more of the details and as generally shown in FIGS. 1-4, aschematic of a nanowire core-shell radial heterojunction solar cell isshown. Referring more specifically to FIG. 1, one illustrative exampleof a solar cell device 20 is provided. The device 20 includes aplurality of nanowire cores 22 having a coating 24 thereon. In one form,the coating 24 extends over the tops of the nanowire cores 22, such asillustrated at reference 26. FIG. 1A shows an enlarged view of a portionof one nanowire core 22 and coating 24.

The device 20 also includes a first electrode 30 and a second electrode32. In one form, the first electrode 30 includes a substrate 34, whichmay be provided for growing the nanowire cores 22. The first electrodemay include any number of additional materials and layers so as toimprove overall electron transport and/or decrease resistance. Forexample, the first electrode 30 may include a contact layer 36 forproviding suitable contact between the substrate 34 and other componentsin the first electrode 30 or elsewhere in the solar cell 20. The firstelectrode may also include a collector 38, such as used to collect andtransfer electrons at the first electrode 30.

The second electrode 32 may similarly include one or more differentmaterials and/or layers. The second electrode 32 is generally providedso as to allow light and/or photons to pass through at least a portionof the electrode 32. As shown in FIG. 1, the second electrode 32 is inthe form of strips or other interconnected designs so as to allow lightand/or photons to pass in-between. In other forms, the second electrodecan include at least a portion that is transparent, translucent, and thelike.

In one form, the device 20 includes an insulating layer 40 at the endsof the nanowire cores adjacent the first electrode 30. The insulatinglayer 40 generally prevents the coating 24 from contacting the substrate34 and/or portions of the first electrode 30. If the coating 24 were tocontact the first electrode, it could cause a short circuit in the solarcell.

FIG. 2 illustrates a side view of the solar cell device 20. As shown inthis figure, light, as represented by arrow 50, passes at leastpartially through the second electrode 32 to interact with the coating24.

FIG. 3 illustrates a similar solar cell device 52 as shown in FIG. 2. Indevice 52, the substrate 34 and/or first electrode 30 include a maskinglayer 54. Masking layer 54 may be used temporarily, such as duringmanufacture, or permanently, to prevent nanowire cores 22 from growingon all sides of the substrate. The specifics of masking layer 54 and usethereof will be discussed in further detail below.

FIG. 4 illustrates another form of solar cell device 60. This device 60includes an electrode component 62 that can be used as part of and/or inconjunction with the second electrode 32. The electrode component 62 caninclude a material that is at least partially transparent and/ortranslucent. The electrode component 62 can be placed on the secondelectrode 32, below the second electrode 32 and/or at least partiallyextend beyond the second electrode 32 to contact the coating 24. Forexample, in the form of a masked second electrode 32 as shown in FIG. 1,the electrode component 62 can pass between the spaces in the secondelectrode 32. Further, the electrode component 62 can extend along thelength of the nanowire 22 and coating 24 to provide further contacttherebetween. The electrode component 62 and use thereof will be discussin more detail below.

There are a variety of different materials that may be used in the solarcells described herein. In general, the coating(s) comprise graphene andgraphene related materials. For example, the coating may comprisegenerally a single layer of graphene or a few layers of graphene. Inother forms, the coating material may comprise reduced graphene oxide.In this regard, depending on the application method, multiple layers ofreduced graphene oxide typically result as the coating.

Graphene consists of a single layer of carbon infinitely extended in twodimensions. The chemical bonds between the carbon atoms are very similarto those in graphite. Graphene has an electronic structure that impartsunique optical and electrical properties not found in any othermaterial. Importantly, graphene absorbs light more strongly than anyother material and does so independent of wavelength throughout theentire solar spectrum. Unsupported graphene has no bandgap and electronsbehave as if they were massless fermions. At the so-called Dirac point,coincident with the Fermi level, the density of quantum states is zero.Because electrons move with a velocity that is a sizeable fraction ofthe velocity of light, graphene follows the dictates of quantumelectrodynamics rather than quantum mechanics.

The nanowire cores may also include a variety of different materials.For example, a variety of wide bandgap materials may be used. Such widebandgap materials may include, but are not limited to, zinc oxide,boron, titanium, silicon borides, carbides, nitrides, oxides, orsulfides, combinations thereof, and the like. Wide band-gap materialwill be understood to refer to a material having a valence band and aconduction band that differ by at least two volts. In one form, zincoxide may be especially suitable for at least some of the techniques andcombinations of materials discussed herein.

Zinc oxide possesses outstanding optoelectronic properties. For example,density functional calculations have shown that there is a strongattractive potential, enhanced with nanowires, between zinc oxide andgraphene due to a dipole induced dipole electrostatic interactionaccompanied by only a small degree of electron transfer. This “contact”interaction profoundly changes certain of graphene's electronicproperties such as the work function while leaving the desirableelectronic structure and other electronic properties such as the Diracpoint of graphene intact. It turns out that the work function of widebandgap ZnO (3.37 eV) is also very surface sensitive and increases by upto 2.8 eV when placed in contact with selected substances. Thus, thework function of graphene decreases while that of zinc oxide increasesas a result of contact between the two materials allowing graphene tofunction as a photoactive material. The work function changes are due toa redistribution of charge that occurs when graphene comes into contactwith ZnO, with the graphene interacting with ZnO in just the requisitemanner, perhaps because its ambipolarity allows it to act as an electronacceptor.

The solar cell devices disclosed herein were developed to test theconjecture that, based on these theoretical considerations, theresulting large difference in work functions might make the graphene/ZnOjunction favorable for charge separation. The results disclosed hereinof the experimental tests undertaken to test those conjectures confirmthat graphene/ZnO heterojunctions are in fact capable of giving rise tolarge photocurrents as well as photovoltages and are good candidatematerials for a new generation of high conversion efficiency solarcells.

As elucidated more fully in the discussion below, the applicant hasdeveloped a novel heterojunction solar cell architecture and relatedfabrication methods based on a p-n junction, such as in the form of zincoxide nanowires radially clad with a single layer or up to a few layersof graphene or reduced graphene oxide. The ZnO nanowires provide for ahigh voltage and facilitate current transport, and the graphene materialabsorbs the entire spectrum of sunlight and creates the current aselectrons are accelerated into the ZnO nanowire cores. The graphenematerial is contact charged by the redistribution of electric charge atthe graphene-ZnO interface, resulting in an increase of the workfunction of ZnO and a decrease of the work function of graphene. The“effective work function” of the solar cell, constituting the differencein the work functions of the materials forming the p-n junction of thecell, is therefore increased and consequently the solar cells operate atsignificantly higher voltage levels than have previously been achievedin silicon based or other prior solar cell architectures.

As further described and demonstrated below, the present teachingsenable the production of photovoltaic solar cells displaying an opencell voltage in excess of 2.4 V and as high as at least 3.5 V. Withoptimizations related to improve series resistance, coating uniformityand recombination kinetics, the disclosed architecture should providephotocurrent levels resulting in conversion efficiencies that farsurpass that of cells used in present day photovoltaic installations.

In one approach, the nanowire cores are formed of a material thateffectively distributes charge to graphene upon contact, resulting inincreasing the material's work function while reducing the work functionof graphene. Suitable core materials may also have an attractivepotential with graphene causing them to be catalysts for the thermaldecomposition and simultaneous conversion of one or more aromatichydrocarbon precursors to form one or more layers of the graphene shellcladding the nanowires. The shells/coating 24 comprise a graphenematerial, which, in a preferred form, comprises graphene or reducedgraphene oxide, and are preferably conformally disposed about at least asubstantial portion of the cores 22. As used herein this reference to“substantial portion” will be understood to refer to an amount disposedabout more than fifty percent of the nanowire surface area. Generallyspeaking, a viable solar cell will comprise a plurality of such nanowirecores 22 that each have a shell 24 of a graphene material disposedthereabout.

In one approach, the nanowire cores comprise zinc oxide. In other forms,zinc oxide constitutes about 50 to about 100% of the nanowire cores. Asused herein, “consist substantially of” a material will be understood torefer to an amount in excess of fifty percent. In one form, the nanowirecores consist substantially of zinc oxide such that at least fiftypercent of the nanowire cores is zinc oxide. The reference to the core22 consisting essentially of a material will be understood to refer to acore 22 that is largely pure in these regards but which can includetrace impurities and dopants, for example, purposefully-introducedn-type or p-type dopants designed to elicit desired electricalproperties.

The nanowires are generally arranged on the foil such that they extendtherefrom in a generally transverse manner. In a preferred form, thenanowires can be disposed so that at least a majority of the nanowireshave their longitudinal axes substantially aligned to one another andextend generally perpendicular to the foil. As used in these regards,“substantially aligned” will be understood to mean within twenty-fivedegrees and “generally perpendicular” will be understood to meanextending at an angle of between 70 degrees to about 110 degreesrelative to the substrate. In particular, by one approach theselongitudinal axes are also oriented substantially coaxial and parallelto anticipated light beams.

The bottoms of the resulting nanowire nanostructures are attached to thefoil substrate 34, thus electrically connecting all of the cores 22. Thetops of the nanowires carry layers of a coating, such as the graphenematerial, that are in electrical contact with all of the coaxial shells24 surrounding the nanowire cores 22. The growth process thusautomatically creates a solar cell nanostructure that provides separateelectrical connections to cores 22 and shells/coatings 24.

The thickness of these shells/coating of graphene material 24 can varywith the application setting. To maximize the cell voltage, however, thethickness is preferably from about one layer to a few layers.Accordingly, for many purposes the thickness of the shell 24 is verythin. Generally speaking, when employed in a photovoltaic setting, thenumber of layers need be no more than are required to achieve aparticular amount of light absorption. It will be presumed herein thatthe shell 24 has an essentially uniform thickness for a given object butthese teachings will accommodate variations in these regards if desiredand/or as appropriate to the needs of a given application setting. Forexample, in some application settings it can be useful if the shell 24has no more than about ten layers of the graphene material. In apreferred form the graphene material is graphene that is substantially 1atom thick and in other forms the thickness ranges from 1-3 layers thickalong the length of a nanowire. When the graphene material is reducedgraphene oxide (r-GO), the preferred thickness is 2-10 layers thick.

By one approach, dark current and majority carrier transport can beminimized by preventing contact of the coaxial graphene material shells24 with the foil substrate 34. This can be accomplished, for example, bychemical vapor deposition of a monolayer or multilayers of an insulator40 in the spaces between the nanowire cores 22 prior to depositing thegraphene material shells 24. Alternatively, the insulator layer 40 maybe formed during hydrothermal growth of the nanowire cores themselves,as is described further below.

A solar cell apparatus in accordance with the design illustrated in FIG.1 and utilizing an array of ZnO nanowires can take advantage of theunique optoelectronic properties of ZnO nanowires. Bulk ZnO is aninsulator and although it is possessed of a quite sizeable electronmobility, it has generally been considered unsuitable as a solar cellmaterial due to its relatively high resistivity. Nonetheless, bulk ZnOdisplays a very limited electron transport due to surface electricalconductivity. By structuring the ZnO in the form of nanowires, thesurface electrical conductivity is vastly enhanced, presumably becausethe surface to volume ratio of the nanowire form is orders of magnitudelarger than that of the bulk form. Compared to bulk ZnO, nanowires ofthis material are quite good electrical conductors.

Single layer graphene absorbs 2.3% of solar radiation and does soindependent of wavelength from the infrared to the ultraviolet regionsof the spectrum. The ZnO nanowires are preferably clad uniformly alongtheir entire length with graphene to insure optimal absorption of solarradiation. In order for single layer graphene cladding to absorb all ofthe incident solar radiation, the graphene clad area must exceed thelinear area by at least a factor of 43. By cladding nanowires withgraphene, the graphene area exposed to sunlight is easily increased bytwo orders of magnitude compared to the “linear” area of the cellitself. In one aspect, the nanowire diameters and aspect ratios arechosen so as to fulfill this requirement. Thus, the nanowires thatcomprise the nanowire cores may have a longitudinal length in excess ofmany hundreds of nanometers. For example, the length of the nanowirescan range from about 5 to about to about 25 micrometers, and the lengthof the individual nanowires may vary somewhat in a given solar cell. Thelength of the nanowires can be adjusted by changing the concentration ofthe starting materials. The cross-sectional diameters of the nanowiresare preferably from about 40 to about 500 nanometers, although theseteachings will accommodate nanowires of other diameters. The nanowirecores may be characterized by an aspect ratio (length divided bydiameter) of from about 10 to about 250.

The creation of such core/shell axial heterostructures allows absorptionof the total solar flux on a substantially reduced “linear” area ofsolar cell material. Each one of the vast numbers of such nanowirespresent in such a photovoltaic device comprises a unique structure thatindividually acts as an effective nantenna and optical rectifier.Calculations for cylindrical nanowires of radius twenty nanometers showthat total light absorption occurs for nanowire lengths of about fourhundred nanometers (which is, in turn, in the range of the wavelengthsof visible light). Each nanowire can therefore be seen to simultaneouslypossess both the light (electromagnetic wave) gathering power of anantenna and the rectifying properties of a photovoltaic device.

The areal density of the nanowires may also be optimized to manipulatethe optical and electrical performance of the solar cell devicesaccording to the teachings herein. In this regard, areal density may becharacterized as the number of nanowires per area of substrate, or asthe proportion of the substrate area occupied by nanowires. The arealdensity may be determined, for example, from measurements of nanowirediameter and distance between nanowires obtained from SEM images of thenanowire array.

The areal density of the nanowires may be controlled by manipulatingfactors such as the chemistry of the precursor solution, temperature atwhich the nanowires are grown, concentration of the nucleation speciesused, surface roughness and crystallinity of the seed layer, and otherconditions, as is understood by those skilled in the art of hydrothermalgrowth of nanowire arrays. In one form, the nanowires are grown suchthat there is a high areal density of nanowires thereon. It is generallypreferable that the nanowire array be as dense as possible to maximizethe power output per area of the solar cell device. However, if theareal density is too high, coating the nanowires uniformly with graphenealong a substantial portion of their lengths becomes more difficult. Thedensity and spacing of the nanowires should be as high as possible whileleaving sufficient spacing to be able to coat with graphene and suchthat the adjacent coated nanowires do not contact one another so as toprevent short circuiting the solar cell. In one form, the areal density,in terms of the percentage of the substrate area in contact with thegrown nanowires prior to coating with graphene, is approximately 10% toabout 80%, though it may be more, if appropriate.

Hydrothermal synthesis processes to form ZnO nanowire arrays on manydifferent metal foils are understood by those skilled in the art. Thefoil substrate can thus comprise a variety of metals, including, forexample, zinc, aluminum, steel, or copper, to note but a few examples inthese regards. The thickness of the foil can vary with the applicationsetting. For many purposes, the thickness of the foil is very thin tomake the solar cell apparatus flexible so that it can cover surfaces ofa variety of shapes. Generally speaking, however, a thicker foil willhave greater strength. For many applications, the foil is thin enough tobe flexible yet thick enough to avoid being torn or ruptured in use.These teachings will accommodate variations in the selection of foilmaterial and the foil thickness if desired for cost or other reasonsand/or as appropriate to the needs of a given application setting.

By one approach, the substrate is provided as a zinc foil and ahydrothermal synthesis process is used to form an array of substantiallyaligned zinc oxide nanowires to serve as the nanowire cores 22. The ZnOnanowires need to be in ohmic contact with the first electrode. In oneapproach, this can be accomplished using hydrothermal synthesis on zincmetal foil using an aqueous solution of zinc acetate and hexamine. Thepresence of hexamine (hexamethylenetetramine) promotes highlyanisotropic growth conditions because of selective capping of thenon-polar ZnO crystallographic planes. As one illustrative example inthese regards, but without intending to suggest any particularlimitations in these regards, aligned ZnO nanowires can be grown usingan aqueous solution of 50 mM zinc acetate and 50 mM hexamine in contactwith 100 micron thick zinc foil at 90 degrees centigrade for 4 hours.Using this approach, nanowires were 100 to 200 nm in diameter and 10 to15 microns in length, and a substantially continuous coating of anonconductive zinc oxide formed on the foil substrate between the ZnOnanowire cores.

In another approach, ZnO nanowires could be grown at elevatedtemperatures using water as a source of oxygen, such as used in theprocess of zinc galvanization. In yet another form, a seed layer can beused to grow the nanowires.

FIG. 6 is a field emission scanning electron microscope image taken fromone end of a ZnO nanowire array formed in this manner. The nanowireshave a hexagonal cross-sectional geometry and are substantially alignedalong their longitudinal axis. Inelastic scattering-based Ramanvibrational spectroscopy analysis of such ZnO nanowires is presented inthe lower portion of FIG. 9. The E2 vibration mode peak at 438.78 cm⁻¹of the lower curve is indicative of substantially pure ZnO.

If the hydrothermally grown nanowires are too long, their ends maydiverge outwardly in a characteristic “flower” growth pattern shown inthe center region of the FESEM image of FIG. 18. Although notnecessarily detrimental to the cell performance, this is preferablyavoided as it may increase the difficulty of coating the nanowiresuniformly with graphene.

In order for the foil to function as an electrode, one side should beprotected from nanowire growth. This can be accomplished by protectingone side with a polymer film or coating, prior to forming the nanowirearray, such as shown as masking layer 54 in FIG. 3. The protectivepolymer coating is subsequently removed, typically after cladding of thenanowires with the graphene material, such as by dissolution using oneof a number of different organic solvents. In one form, this techniquewas deployed using polymethylmethacrylate (PMMA) to protect one side ofa Zn foil from ZnO nanowire growth. Any alternative plastic coating orfilm capable of withstanding the temperature conditions of the nanowiregrowth and cladding steps can be used.

An alternative method for preventing the growth of nanowires on bothsides of a foil is to double the foil so that two sides touch. Growthsolution is prevented from reaching the protected sides allowing growthof nanowires to occur exclusively on the two exposed sides. Aftercladding the nanowires with a graphene material, the doubled foil isrestored to its single foil form.

The power output of a solar cell being a function of current, it ispreferable to minimize the series resistance of the cell. Seriesresistance in a solar cell is a combination of the resistance to currentflow through the emitter and base of the solar cell, the contactresistance between the electrodes and the materials of the photovoltaicjunction, and the resistance of the electrodes. The sheet resistance ofthe nanowire array is a principal contributor to the series resistanceof the solar cells disclosed herein. Sheet resistance is used tocharacterize the resistance to current flow along the surface of asheet, not perpendicular to it.

By one approach the nanowires 22 can be subject to a post-growthannealing process to thereby reduce surface defects and increase thesurface conductivity thereof in a controlled way. The annealingprocedure may consist of heating the nanowire/foil composites in anoxygen atmosphere or by using other conventional techniques. FIG. 15shows the effect of annealing of ZnO nanowire arrays in an oxygenatmosphere at 350° C. for up to eight hours prior to cladding withgraphene. The nanowire array of approximately 1 cm² was formed and itssheet resistance was measured directly by using a conventionalfour-point probe measuring device. The sheet resistance had decreasedsubstantially after 2 hours of annealing and by up to two orders ofmagnitude after 8 hours.

Further decrease in series resistance will result in a proportionateincrease in photocurrent. It is believed that this may be achieved byannealing at temperatures higher than 350° C. For example, such highertemperature annealing can be performed despite zinc's relatively lowmelting point (about 420° C.) by contacting the zinc foil substrate withcopper foil to form brass by diffusion raising the melting point andallowing the further reduction of surface defects on the zinc oxidenanowires at the higher temperature conditions.

Post-growth annealing may also improve the diode properties of thenanowires. As will be appreciated, the p-n junction formed by claddinggraphene radially about a ZnO nanowire functions as a diode thatconducts current primarily in one direction. The ZnO starts out as ann-type semiconductor, but when in contact with graphene material the ZnOtransfers excess electrons to the graphene and the graphene becomes ann-type region that contains negatively charged electrons and ZnO becomesa p-type region that contains positive charge carriers. As is confirmedby experimental investigations presented in more detail below, thegraphene coating absorbs photons of sunlight and a flow of electronsoccurs from the graphene to the ZnO.

The impact of oxygen annealing has also been shown to significantlyimprove the cell rectification factor. In this regard, the cellrectification factor is understood to refer to the ratio of the forwardto the reverse current. In one study performed for the r-GO/ZnOheterostructure before and after O₂ annealing for 8 hours at 400° C.,the rectification factor increased from 0.52 to 1.82 (4-fold increase),indicating a much higher forward current than the reverse saturationcurrent. Having a good rectification factor influences the ideality ofthe fabricated diode for optoelectronic applications. Lower reversesaturation currents are preferred to avoid leakage current and lessobserved voltage under solar insolation.

In another aspect, doping of the nanowire cores 22, such as by additionof dopants to the growth solution, may be used to increase theelectrical conductivity thereof in a controlled way as one technique forreducing the series resistance of the solar cell apparatus. In oneaspect, one or more dopants are included along at least a portion of thelongitudinal surface thereof. Dopants may include, but are not limitedto at least one of aluminum, indium, chlorine, and gallium. Such anapproach to doping can help to optimize the characteristics of thejunction between the nanowire cores and the coating, such as thegraphene-zinc oxide junction, to yield a solar cell that displaysmaximum efficiency with respect to converting light to electricity.

After formation and any subsequent annealing and/or doping steps, thealigned zinc oxide nanowires 22 can be exposed to a cladding procedureto deposit a graphene material along the longitudinal surfaces in thespaces between the wires as well as on the top surfaces of the nanowirecores 22 themselves. By one approach, this coating or shell 24 mayconsist primarily of reduced graphene oxide and/or graphene andcomprises, for example, from a few layers to no more than about tenlayers in thickness. For example, Hummers method (W. S. Hummers and R.E. Offeman, JACS 1958) can be used to synthesize few layer micrometersized flakes of graphene oxide (GO) to be used as a cladding for the ZnOnanowires. Graphite is treated using well-known procedures involvingnitric and sulfuric acids together with KClO3 or KMnO4 as oxidizingagents to make graphene oxide (GO).

Cladding of the ZnO nanowires may proceed by drop-casting an aqueoussuspension of graphene oxide onto an array of aligned ZnO nanowires,followed by heating to a temperature of about 300° C. in a hydrogenenvironment for about 2 hours. Various other methods such as drop, dipand spin coating can alternatively be used to surround the nanowireswith graphene oxide. The GO flakes are reduced thermally by heating in ahydrogen atmosphere. Some oxygen remains in substitutional sitesyielding reduced graphene oxide, a disordered form of a few layers ofgraphene. The uniformity of the cladding is enhanced by adding isopropylalcohol or acetone as wetting agents to the aqueous suspension prior todrop-casting. In order to prevent short circuits from occurring, it isdesirable that the reduced graphene oxide does not come in contact withthe Zn foil or substrate carrying the ZnO nanowires.

Other methods for surrounding the ZnO nanowires with a thin coating ofr-GO are also possible. For example, known methods for solubilizing r-GOflakes to form a solution or to make a colloidal suspension of r-GOflakes can be used so that the nanowire coating process can be performedfrom a solution. In such an approach, the solution or stable colloidalsuspension of r-GO flakes is applied to the nanowires and the solventallowed to evaporate with optional heating to remove impurities.Alternatively, such an approach can be used to coat the nanowires withgraphene from a solution of graphene nanoflakes.

FIG. 7 is a field-emission scanning electron microscopy ofhydrothermally grown and oxygen annealed ZnO nanowires coated with r-GO.The FESEM topography characterization showed an approximate length ofabout 10 microns which were vertically aligned with some horizontalwires residing on top of the parallel vertically ordered ZnO nanowires.The cladding of r-GO is clearly observed as a transparent thin layerwrapping around ZnO nanowires and covering the top surface as well asyielding good interfacial contacts with the semiconductor. The coatednanowires are more round compared to the hexagonal uncoated nanowires,indicating that the r-GO coating is several layers thick.

Raman vibrational spectroscopy analysis was also carried out toillustrate the existence of both ZnO cores and r-GO shells in theco-axial hetero-architecture. One such spectra is presented in the topspectra in FIG. 9. The ZnO samples showed the corresponding ZnO peaks E₂^(low) and E₂ ^(high) due to in-plane vibrations of Zn—O bonds. Ther-GO/ZnO heterostructure exhibited the in-plane vibrations-based E peaksas well as the A peaks attributed to out-of-plane vibrations of Zn—Obonds. Moreover, the defect-induced “D” and graphitic “G” modes whereobserved in the r-GO/ZnO nanocomposite indicating the presence of r-GO.

The r-GO clad ZnO nanowire heterojunction photovoltaic cells with asilver electrode patterned as generally shown in FIG. 1 in contact withthe r-GO in accordance with the principles disclosed have attained opencircuit voltage of up to about 2.4 V, which is significantly higher thanthat possessed by any previously single junction solar cell of which theapplicant is aware. By comparison, the open cell voltage of siliconbased solar cells typically does not exceed 0.6 V. The current densityvs. voltage profile of five such cells illuminated with 1 KW/m² of AM1.5G irradiation is presented in FIG. 11. As will be appreciated, AM1.5G is a standardized light spectrum that approximates overall yearlyaverage solar irradiance for mid-latitudes in the United States and isused by the solar industry for standardized testing or rating ofterrestrial solar cells or modules. (The latest AM 1.5G standardspertaining to photovoltaic applications are reflected in ASTM G-173 andIEC 60904.) The current and voltage profile was generated by use of astandard Keithley Source Meter. The observed differences between thecurrent density and voltage profiles of the individual cells are likelyattributable to factors such as variance of the r-GO coating uniformityand/or of the dimensions and density of the nanowires.

The large open-circuit voltage (i.e., the voltage when overall currentflow through the solar cell is zero) observed can be rationalized basedon a very large work function increase reaching 2.8 eV that occurs whenZnO is in intimate contact with a strong electron acceptor. Graphene,because of its amphoteric character, can serve in this capacity with ZnOacting as the electron donor. Owing to the interfacial charge transferbetween r-GO and ZnO, the ZnO donates electrons to graphene. Therefore,the work function of ZnO increases about 1 eV and for r-GO it decreases.Upon illumination, photons generate excitons (bound electron-hole pairs)in the exterior r-GO shell and exciton dissociation take place at theheterojunction due to the existing built-in electric potential. Theelectrons transport from the low work function graphene to the largework function ZnO.

The investigations underlying the disclosure herein have also confirmedthat graphene functions as the photoactive element by following thephotocurrent as a function of wavelength. As shown in FIG. 16, thenormalized photocurrent (i.e., the current corrected for sensitivity ofthe phototube measuring device) generated from the heterostructure issubstantially constant over a broad wavelength range from 200 to 1100nm. This indicates that exciton generation takes place in r-GO since ZnOdoes not absorb light in the visible region of the spectrum. The r-GOcan absorb all the sunlight energies corresponding to a UV-Vis-1Rwavelength ranging from 200 to 1100 nm and into the IR. The maximumabsorption for r-GO occurs at 290 nm which is located in a UV region;however, most of sunlight energy is actually in the visible region andcan only be absorbed by r-GO in the ZnO/r-GO heterostructure.

Since the normalized current data shows a stable photogeneratednormalized current of 0.6-0.7 from 200 to 1100 nm, one may conclude thatuniform r-GO clad ZnO nanowires result in solar energy absorption acrossthe whole solar spectrum to generate observed wavelength independentphotocurrents. The use of ZnO nanowires without graphene cladding wouldnot yield a significant photo current due to the fact that ZnO is awide-band gap semiconductor (3.37 eV) requiring sunlight in theultraviolet part of the spectrum to photoexcite ZnO orbital electronsfrom the valence to the conduction band in order to generateelectron-hole pairs. Since essentially all of the solar spectrum lies atenergies lower than the ultraviolet, the electron excitation to formelectron/hole pairs occurs essentially only in graphene. Chargeseparation occurs at the junction of graphene with ZnO yieldingphotocurrent at a cell voltage up to 2.4 V.

The experimental results displayed in FIG. 17 show that the magnitude ofthe photocurrent is linearly dependent on light intensity over a rangeof three orders of magnitude. With the AM 1.5G light source aphotocurrent of 4.14 μA is generated compared to a photocurrent of 3.46nA produced when using monochromatic light. The AM 1.5G light sourceincludes all wavelengths of the solar spectrum. Its intensity wasmeasured to be three orders of magnitude higher than the light intensityof the monochromatized source.

Yet another aspect of the invention involves enhancing the open cellpotential by contacting at least a portion of the outer surface of thecoating or shells, such as r-GO shells (i.e. the surface facing awayfrom the ZnO cores), with a material that functions as an electron donorto graphene. In one preferred aspect, the electron donor material mayalso function as a current gathering electrode. Such an electrode may beformed, for example, by depositing a paste of silver nanoparticlesthrough a patterned mask that had been placed on the r-GO terminatedsurface of the cell. In the illustrated embodiment of FIG. 1, the metalis patterned as a series of spaced, elongated fingers extendingperpendicularly from a bus bar, which allows for sufficient surfacecontact between the metal and the r-GO shells. A prototype of a 1 cm²cell is displayed as FIG. 5, which shows the top of the cell with asilver layer contacting the top surface of the r-GO coated ZnO nanowirearray. Sunlight illuminates the graphene by penetrating between thenarrow silver fingers. The metal layer may be provided in othergeometries that can similarly function to create a surface contact withthe r-GO shells while allowing sufficient sunlight penetration. In thisway advantage is taken of the substantial photon absorptioncharacteristics of the nanowire array clad with r-GO that constitutesimportant constituents of the solar cell device.

Silver acts both as an n-type contact dopant and as an electrode. Thesilver electrode was effective to increase in the open circuit potentialto about 2.4 V. While not wishing to be limited to any theory, thiseffect may be the result of a similar redistribution of charge betweenthe metal and r-GO resulting in contact charging that decreased the workfunction of the r-GO shells by an amount that corresponds to theobserved increase in the cell open circuit potential. As discussedbelow, this effect has also been demonstrated in alternative embodimentshaving shells of substantially single layer pure phase graphene producedfrom polyaromatic precursors. Indeed, by judicious contacting of thesingle layer graphene/ZnO nanowire/silver composite the open circuitvoltage was found to have been increased to 3.5 V. Further, it isbelieved similar improvements can be made with other nanowire corematerials as well as by using other electron donor contact chargingmaterials that can simultaneously function as electrodes.

Thus, by one approach, both sides of the graphene-based shells are usedto lower the graphene work function and thereby increase the open cellpotential. In such embodiments, the graphene coating or cladding is inessence being charged by two “plates” to develop giant built-inpotential. Although the significant performance benefit of thisimportant discovery has been demonstrated using silver, other metalssuch as aluminum, copper, and others in reducing the work function ofgraphene by donating electrons to graphene. In addition, materials suchas ZnO could also be used as the contact charging material in the doublecontact charging configuration disclosed herein. The teachings hereinwill enable those skilled in the art to identify other suitablealternative contact charging materials by comparison of cell voltagemeasurements of solar cells made with and without the candidate materialin contact with the graphene material shells.

The arrangements for implementation of double contact charging are notlimited to contacting the electron donor with the ends of the nanowiresas illustrated in FIG. 1. For example, the electron donor mayalternatively be arranged so as to contact positions along the length ofthe nanowire. Combinations of these approaches may also be effective.According to another aspect, described in more detail below, the chosencharging material is incorporated within another material, such as anorganic or inorganic transparent electrode conductive material, thatfunctions as the electrode for the graphene side of the photovoltaicjunction.

Turning back to approaches for cladding the ZnO nanowire cores inaccordance with the disclosure herein, in another approach, thenanowires are clad with an ultra-thin coating, consisting of singlelayer to no more than a few layers, of graphene. Polyaromatichydrocarbons (PAH) such as coronene, pentacene, naphthalene and othersthermally decompose on metals such as copper to form single layergraphene at modest temperatures. It was not known, however, whethersimilar results could be obtained with ZnO nanowires. Additionalinvestigations have led to the discovery of techniques utilizing theseprecursors that are effective to deposit one to a few layers ofessentially pure phase graphene substantially uniformly alongsubstantial portions of the outer surface of the ZnO nanowires.

As an illustrative example of this newly developed cladding technique,coronene was dissolved in tetrahydrofuran and drop-cast onto ZnOnanowire arrays hydrothermally grown on Zn foil. These assemblies wereheated in an argon atmosphere at temperatures between 200° C. and 400°C. for one to two hours. A thin layer of this solution in contact withZnO decomposes to form graphene and the remainder evaporates.

With reference to FIG. 10, Raman spectroscopic examination revealed thatthermal decomposition had indeed resulted in the formation ofhigh-quality graphene as evidenced by G/D band intensity ratios of about2.0. Electron microscopy images of the clad nanowires, such as the imagedisplayed in FIG. 8, show that the hexagonal facets of the nanowires arepreserved suggesting that growth of single layer graphene has occurred.The discovery disclosed herein of a solution to overcoming the difficultchallenge of cladding with graphene billions or even trillions ofdensely packed nanowires has significant implications for the commercialscale production of high efficiency solar cell devices. It is believedthat the very strong attractive potential of about 1 V that has beenshown by theoretical density functional calculations to exist betweengraphene and ZnO lowers the activation energy for the transformation ofPAHs to graphene and becomes, in a sense, the driving force for thereaction. The ZnO surface can be thought of as functioning as acatalytic surface for the reaction enabling the formation of anultrathin layer of graphene on a nanowire structure, and at temperaturesas low as 200° C. The reaction is self-limiting because once thegraphene layer forms on the surface it remains there rather than leavingthe ZnO surface to allow the next PAH molecule to be catalyzed. Whilethe above description uses ZnO, it is believed that other wide band gapnanowire core materials may also be suitable for use in this manner.

Based on the insights derived from this work, other aromatic molecules,such as substituted benzenes, are also believed to be suitableprecursors to clad ZnO nanowires with an ultrathin coating of from oneto a few layers of graphene according to the teachings herein. Thistechnique is also adaptable to nanowires formed of other materials thatexhibit attractive potential with graphene, as can be identified bytheoretical density functional calculations.

This disclosure of a technique for coating high density nanowire arrayswith an ultrathin coating of graphene has significant implications forthe production of high efficiency solar cells. The open circuit voltageof such graphene clad ZnO nanowire solar cells was observed to be about1.9 V under 1 KW/m² of AM 1.5G illumination, even without contactcharging the graphene with a metal electrode to decrease its workfunction. In combination with a silver electrode in contact with thegraphene shells, open cell potentials as high as 3.5 V were observed.The higher cell potentials achieved in such solar cell devices comparedto those clad with r-GO are believed to be due to the higher graphenequality of single or few layer graphene produced from polyaromatichydrocarbons. Since contact charging is an electrostatic phenomenon,charges transferred from the metal layer are distributed over a singlerather than over several layers of graphene. The transferred charge cantherefore be expected to result in a higher graphene charge density. Inthis way, the built-in potential is increased resulting in the observedincrease in the open circuit potential.

The ultrathin graphene coating obtained by thermal transformation ofpolyaromatic hydrocarbons decreases the width of the junction to about2-3 angstrom compared to about 8-9 angstrom for ZnO nanowires clad withseveral layers of r-GO. This, in addition to higher graphene quality,may be another reason for the superior functioning of single layergraphene in this photovoltaic device.

In yet another aspect, graphene shells may be doped to further controlthe graphene work function. In particular, doping the shells with n-typedopant such as nitrogen, by heating in an ammonia atmosphere forexample, or other n-type dopant, can further reduce the work function ofthe graphene by at least 0.5 V, which may enhance the open circuitpotential even more. It should also be kept in mind that it is unlikelythat the open circuit voltage to exceed the band-gap of the materialconstituting the nanowire core.

The creation of a graphene-based nanocomposite photovoltaic devicedisplaying an open circuit voltage as high as 3.5 V enables a new classof potentially high efficiency solar cells. In addition to high opencircuit voltage, high short circuit currents are necessary to achievehigh power conversion efficiency. As discussed above, since currentflows on the surface of the ZnO nanowires, the current density can beenhanced by controlling the nanowire growth conditions to increase thesurface to volume ratio of the nanowires by reducing their diameter.

Another factor believed to affect the short circuit currents of devicesfabricated in accordance with the disclosure herein relates toelectron/hole recombination kinetics. Exciton lifetimes in have beenreported to not exceed a few femtoseconds in pristine graphene.Recombination kinetics could strongly compete with electron transportacross the heterojunction. To address this, an appropriate dopant may befound which act to increase exciton lifetimes and thus increase thephotocurrent. The inclusion of one or more of such dopants in thegraphene or r-GO shells can result in more favorable electron/holerecombination kinetics and increase the photocurrent produced by thedisclosed solar cell devices.

In another aspect, the photocurrent performance of the solar cell devicemay be optimized by the inclusion of conductive material to establishelectrical contact between the nanowires. Transparent conducting oxidessuch as indium tin oxide (ITO), or ZnO based conducting transparentoxides or sulfides, for example, can be effective for this purpose andmay be disposed between the nanowires. Indium tin oxide was chosenbecause it is readily available. It was deposited as a thin film by dropcoating. Alternatively, thin films of indium tin oxide can be depositedby many other techniques such as spray coating, or spin coating,physical vapor deposition, electron beam evaporation, or a range ofsputter deposition techniques. Other suitable optically transparentconductors include conductive organic polymers such aspolyethylenedioxythiophene polystyrene sulfonate (PEDOT:PSS) and manyothers, which may be deposited in organic solvents or in aqueoussuspensions.

The conducting material may be located on top of the cell to form all orpart of the counter electrode, and/or in the interstitial space betweenthe graphene or r-GO clad nanowires of the array. In another study, avery substantial decrease in series resistance was achieved by dropcasting a suspension of nanometric indium oxide/tin oxide in isopropanolon the top graphene terminated surface of the nanowire array. In thisway electrical contact was established between graphene clad ZnOnanowires. The resulting impact on cell performance is discussed withrespect to the experimental results described further below.

In another aspect, the transparent conductive electrode material mayinclude a metal effective to reduce the graphene work function, tothereby enhance both the voltage and current density performance of thecell. For example, a colloidal suspension of nanoparticles of silver inITO is applied to the graphene nanowire array to form the electrode andimprove the charge mobility within the array. Alternatively, the silveror another metal may be applied to the graphene coated nanowire arrayfollowed by drop casting a suspension of ITO to fill the space betweennanowires and form a top conductive layer of the solar cell.

Additional experimental results demonstrating the effectiveness of theprinciples disclosed herein in optimizing the photovoltaic properties ofthe radial heterojunction solar cells disclosed herein will now bediscussed. FIG. 12 shows the current density versus voltage profile fora cell having a core-shell heterojunction of graphene wrapped ZnO wiresgrown on zinc foil and coated by hydrothermal decomposition of coronene.In this particular cell, a copper electrode was in electrical contactwith the zinc substrate. ITO was deposited between the nanowires andover the top of the cell to increase the electrical contact between thenanowires and provide the counter electrode for the graphene coating.Each line represents measurements taken by contacting at differentpoints of the cell under 1 KW/m² of AM 1.5G illumination. The data showsthat the cell displayed an open cell voltage as high as about 1.9 V anda short circuit current density in the low mA/cm² range. These resultsshow that the surface interaction between the ZnO and the ultrathinsubstantially pure phase graphene coating generates large cellpotentials even without contact doping the opposite side of thegraphene.

FIG. 14 displays the corresponding current density versus voltageprofile for a photovoltaic cell of a construction similar to that of thecell corresponding to FIG. 12, except that a silver electrode wasapplied to the nanowire array and the ITO was deposited over the silverelectrode. The open cell voltage increased significantly to about 3.5 V,owing at least in part to the effect of silver in decreasing the workfunction of the graphene shells and thereby increasing the differencebetween the work functions of the graphene and ZnO components of theheterojunction.

Further investigations of the effectiveness of the ITO in increasing thephotocurrent were performed by constructing a cell having a graphenewrapped ZnO wire array supported on zinc foil, and a patterned silverelectrode in place of the ITO electrode of the previously describedembodiment. The current density versus voltage profile for this cell isshown in FIG. 13. While the cell displayed an open cell voltage of about3.2 V, its short circuit current density was significantly lower thanthat achieved in the cell with ITO corresponding to FIG. 14. Thesignificantly higher current density shown in FIG. 14 is at leastpartially attributed to the effect of the ITO.

While the principles disclosed herein have been demonstrated with regardto solar cells using ZnO nanowire cores, these teachings are extendableto other wide band gap nanowire materials, for example, boron, titanium,silicon borides, carbides, nitrides, oxides, or sulfides. Wide band-gapmaterial will be understood to refer to a material having a valence bandand a conduction band that differ by at least two volts. The materialsbest suited for generating the highest solar cell potentials are thosefunctioning to contact charge graphene and exhibiting a large attractivepotential with graphene so as to catalyze the formation of single layergraphene shells according to the disclosed aromatic hydrocarbondecomposition method. By additionally contact charging of the oppositesurface of the graphene shell using an electron donor material asdisclosed herein, and the use of a transparent conductive material as anelectrode material for the graphene side of the photovoltaic junction, avariety of high voltage solar cells capable of significantly greaterconversion efficiencies then previously known designs may be provided.

In summary, energy favorable, surface-based, and radial heterojunctionsolar cells made up of graphene 2D layer and ZnO 1D nanowires have beendisclosed. This novel solar cell architecture has been experimentallyshown to be capable of producing an open circuit photovoltage in therange of 2.4 V to 3.5 V under AM 1.5G illumination. While the reportedexperimental results show short circuit currents in the low milliampererange, the broader teachings herein will enable the production of solarcells having short circuit currents of at least 10 mA, and likely ashigh as 25 mA. The creation of a solar cell structure displaying an opencircuit voltage as high as 3.5 V makes it feasible, with additionaloptimizations directed to increasing the photocurrent into the rangejust mentioned, to achieve solar cell energy conversion efficiencies ofat least 50%. The upper limit for the conversion efficiency remains at85% as found determined by non-equilibrium thermo-dynamics. This is farsuperior to the maximum conversion efficiency of about 20% forcommercially available multicrystalline silicon solar cells.Furthermore, the disclosed fabrication methods can be readily deployedin full-scale commercial production at a fraction of the cost of highefficiency multijunction cells based on exotic materials such as galliumarsenide or indium selenide, which are presently available only in lowvolumes at very high price points.

Techniques to increase the photocurrent of solar cells are known in theart, and other principles for generating higher currents within theembodied solar cell devices have been disclosed herein. For example, asdemonstrated in FIGS. 13 and 14, application of the transparentconductor ITO increased the generated photocurrent by three orders ofmagnitude. Selecting the optimum transparent conducting material, oradding colloidal metal particles to increase the electrical conductivityof the ITO, can yield even higher photocurrents. Optimizing thedistribution of the transparent conductive material throughout nanowirearray can also improve the results. Annealing of the nanowires to reducesurface defects has also been shown to reduce the cell resistance.Improvements to the annealing process, such as the higher temperatureannealing techniques described herein, are also expected to reduce theresistance further and yield higher photocurrents. In addition,controlling the diameter and areal density of the nanowires to optimizethe available electron conducting ZnO surface area can increase thecurrent density. One or more of these techniques, or other generallyknown approaches for enhancing the cell conductivity, will enable theproduction of high voltage solar cells having comparatively highconversion efficiencies, achieving significantly shorter energy paybacktimes than conventional solar energy systems.

The discovery of cost-effective high conversion efficiency solar cellsdisclosed herein has enormous beneficial consequences for humanity farinto the future. The sun provides enough energy in one hour to satisfythe energy requirements of the entire global population for a year.Cheap solar power will hasten the day when the sun fulfills its destinyto become the global energy source.

In some forms, it was desired to devise a PV cell that lends itself tolarge scale economical manufacture using non-resource limitedenvironmentally benign materials. In some forms, this may be achieved byemploying hydrothermal growth of ZnO nanowires clad with graphene, apure carbon material. Going from the laboratory sized prototype to largescale development so as to satisfy the world-wide multi-terawatt needfor electricity is a challenging engineering task that is not withoutprecedent. In some forms, the features described herein may be suitablefor achieving these goals.

The novel PV cells described herein can be flexible and readily conformto surfaces of very complex shapes. It is believed that extremelycost-effective retrofitting of the existing PV plants soon to generateone terawatt of solar electricity can be accomplished. Instead of oneterawatt, between three and four terawatts of solar electricity could beproduced at very low cost by taking advantage of trillions of dollarsalready invested in PV installations both as central station plants andas distributed power modules on roof tops.

The flexibility conferred by virtue of using a metal foil substrateopens the door to new markets for PV power generation. For example, theroofs of automobiles may be cited as an obvious application. Other usesand implementations may also be utilized.

Those skilled in the art will recognize that a wide variety ofmodifications, alterations, and combinations can be made with respect tothe above described embodiments without departing from the scope of theinvention, and that such modifications, alterations, and combinationsare to be viewed as being within the ambit of the inventive concept.

What is claimed is:
 1. A photovoltaic solar cell apparatus comprising: afoil substrate; a plurality of nanowire cores on the foil substrate, thenanowire cores comprising a wide band-gap material, wherein at least amajority of the nanowire cores are substantially aligned to one anotherand extend generally perpendicular to the foil substrate andelectrically connected to the foil substrate at a first end of thenanowire cores; a substantially continuous coating of a nonconductivematerial on the foil substrate between the nanowire cores; a pluralityof shells, each comprising graphene material, and each shell beingconformally disposed about a portion of a respective nanowire core toform a plurality of nanowire core/shell structures; a first conductingelectrode electrically connected to the foil substrate and providing afirst electrical pathway to facilitate a movement of electrons away fromthe nanowire cores; a second conducting electrode connected to shells ata second end of the nanowire core/shell structures and providing asecond electrical pathway to facilitate a movement of positive chargesaway from the shells, the second conducting electrode comprising atleast one material effective to reduce the work function of the graphenematerial shells when in contact with the shells, wherein the secondconducting electrode contacts a portion of the surface area of the solarcell at the second end of the core/shell structures while leavinganother portion of the surface area exposed to sunlight.
 2. Thephotovoltaic solar cell apparatus according to claim 1, wherein the atleast one material effective to reduce the work function of shellscomprises one or more of silver, aluminum and copper.
 3. Thephotovoltaic solar cell apparatus according to claim 1, wherein thesecond electrode is in the form of spaced, elongate strips.
 4. Thephotovoltaic solar cell apparatus according to claim 1, wherein secondconducting electrode further comprises a material that is at leastpartially transparent to sunlight and the at least one metal effectiveto reduce the work function of the shells is within at least a portionof the partially transparent material.
 5. The photovoltaic solar cellapparatus according to claim 4, wherein the second electrode the atleast one material effective to reduce the work function of graphene isin the form of particles dispersed within the partially transparentmaterial.
 6. The photovoltaic solar cell apparatus according to claim 4,wherein the partially transparent material of the second conductingelectrode is interspersed between the nanowire cores.
 7. Thephotovoltaic solar cell apparatus according to claim 4, wherein secondconducting electrode comprises indium tin oxide containing particles ofsilver.
 8. The photovoltaic solar cell apparatus according to claim 1,wherein the second conducting electrode is effective to decrease thework function of the shells by at least 0.5 V.
 9. The photovoltaic solarcell apparatus according to claim 1, wherein the wide band-gap materialof the nanowire cores comprises at least one of boron, iron, titanium,zinc, and carbon.
 10. The photovoltaic solar cell apparatus according toclaim 9, wherein the wide band-gap material further comprises at leastone of a boride, a carbide, a nitride, an oxide, and a sulfide.
 11. Thephotovoltaic solar cell apparatus according to claim 1, wherein the wideband-gap material of the nanowire cores comprises at least one of aboride, a carbide, a nitride, an oxide, and a sulfide.
 12. Thephotovoltaic solar cell apparatus according to claim 1, wherein the wideband-gap material of the nanowire cores comprises at least one of zincoxide and titanium oxide.
 13. The photovoltaic solar cell apparatusaccording to claim 1, wherein each shell of the plurality of shells isconformally disposed about a substantial portion of a respective wideband-gap material core.
 14. The photovoltaic solar cell apparatusaccording to claim 1, wherein the foil substrate comprises at least oneof zinc, titanium, brass, steel or copper.
 15. The photovoltaic solarcell apparatus according to claim 1, wherein the shells comprise asubstantially uniform single layer of graphene.
 16. The photovoltaicsolar cell apparatus according to claim 1, wherein the plurality ofnanowire core/shell structures are disposed with their longitudinal axesoriented at least substantially parallel to one another.
 17. Thephotovoltaic solar cell apparatus according to claim 1, wherein thelength of the nanowire core/shell structures of the plurality ofnanowire core/shell structures ranges from at least about 5 micrometersto no more than about 25 micrometers.
 18. The photovoltaic solar cellapparatus according to claim 1, wherein the diameter of the nanowirecores of the plurality of nanowire cores does not exceed 500 nanometers.19. The photovoltaic solar cell apparatus according to claim 1, whereinthe plurality of nanowire core/shell structures are characterized by anaspect ratio of from about 10 to about
 250. 20. The photovoltaic solarcell apparatus according to claim 1, wherein the plurality of nanowirecore/shell structures are characterized by a spatial density of fromabout 10% to about 80%.
 21. The photovoltaic solar cell apparatusaccording to claim 1, wherein the nanowire cores include a dopant alongat least a portion of the longitudinal surface thereof.
 22. Thephotovoltaic solar cell apparatus according to claim 21, wherein thedopant comprises at least one of aluminum, indium, chlorine, andgallium.
 23. The photovoltaic solar cell apparatus according to claim 1,wherein the shells include an n-type dopant.
 24. The photovoltaic solarcell apparatus according to claim 23, wherein the n-type dopantcomprises nitrogen.
 25. The photovoltaic solar cell apparatus accordingto claim 23, wherein the n-type dopant is included in the shells in anamount sufficient to decrease the work function of the graphene materialof the shells by at least 0.5 V.
 26. The photovoltaic solar cellapparatus according to claim 1, characterized in that the photovoltaicsolar cell has an open-circuit voltage of between about 1.5 V and 3.6 Vwhen illuminated with 1 KW/m² of AM 1.5G irradiation.
 27. Thephotovoltaic solar cell apparatus according to claim 1, characterized inthat the photovoltaic solar cell has a short circuit current density ofat least 1 mA/cm² when illuminated with 1 KW/m² of AM 1.5G irradiation.28. A photovoltaic solar cell apparatus comprising: a foil substrate; aplurality of nanowire cores on the foil substrate, wherein at least amajority of the nanowire cores are substantially aligned to one anotherand extend generally perpendicular to the foil substrate andelectrically connected to the foil substrate at a first end of thenanowire cores; a substantially continuous coating of a nonconductivematerial on the foil substrate between the nanowire cores; a pluralityof reduced graphene oxide shells, each shell being conformally disposedabout a portion of a respective nanowire core to form a plurality ofnanowire core/shell structures; a first conducting electrodeelectrically connected to the foil substrate and providing a firstelectrical pathway to facilitate a movement of electrons away from thenanowire cores; and a second conducting electrode connected to thereduced graphene oxide shells at a second end of the nanowire core/shellstructures and providing a second electrical pathway to facilitate amovement of positive charges away from the reduced graphene oxideshells, the second conducting electrode comprising at least one materialeffective to reduce the work function of the graphene material shellswhen in contact with the shells, wherein the second conducting electrodecontacts a portion of the surface area of the solar cell at the secondend of the core/shell structures while leaving another portion of thesurface area exposed to sunlight.
 29. A photovoltaic solar cellapparatus comprising: a foil substrate; a plurality of nanowire cores onthe foil substrate, the nanowire cores comprising a wide band-gapmaterial, wherein at least a majority of the nanowire cores aresubstantially aligned to one another and extend generally perpendicularto the foil substrate and electrically connected to the foil substrateat a first end of the nanowire cores; a substantially continuous coatingof a nonconductive material on the foil substrate between the nanowirecores; a plurality of shells, each comprising graphene material, andeach shell being conformally disposed about a portion of a respectivenanowire core to form a plurality of nanowire core/shell structures; afirst conducting electrode electrically connected to the foil substrateand providing a first electrical pathway to facilitate a movement ofelectrons away from the nanowire cores; a second conducting electrodeconnected to shells at a second end of the nanowire core/shellstructures and providing a second electrical pathway to facilitate amovement of positive charges away from the shells, the second conductingelectrode comprising a material that is at least partially transparentto sunlight and at least one metal effective to reduce the work functionof the graphene material shells within at least a portion of thepartially transparent material, wherein the partially transparentmaterial of the second conducting electrode is interspersed between thenanowire cores.